Hydroforming



March 6, 1956 C. E. HEMMlNGER 2,737,473

HYDROFORMING Filed Feb. 2, 1951 PQODUCT (25cm/Em dba/Zes E ymmz'aer nventor CltftuorrnegA United States Patent OA HYDROFORMING Charles E. Hemminger, Westfield, N. J., assignor to Esso Research and Engineering Company, a corporation of Delaware Application February 2, 1951, Serial No. 209,144

11 Claims. (Cl. 196-49) 'Ihe novel features of the present invention are fully disclosed in the following specification and claims forming a part thereof, read in connection with the accompanying drawing.

Heretofore and prior to the present invention, it was a matter of record and commercial practice in hydroforming, to carry out the reaction in a plurality of reactors each containing a fixed bed of hydroforming catalyst. And in the same connection, it has been known and practiced for several years that due to the highly endothermic nature of the hydroforming reaction that it is desirable and necessary to reheat the product issuing from each stage of a multi-stage hydroforming operation before it enters the next reactor in the series.

The present invention involves an improvement over prior practice in that the catalyst used in hydroforming is in the form of a dense uidized bed in a plurality of reactors operating in series, in each of which, substantially isothermal conditions are maintained due to the nature of the iluidized bed, wherein thorough and intimate mixing of all portions of said bed is achieved.

In the prior hydroforming practice a very severe temperature drop through each reactor occurred. This was especially true, in the lead reactor. Thus, where the feed was fed at a temperature of, say, 1050 F. to the first of a series of xed bed reactors, the temperature drop through this reactor amounted to about 150 F. It can thus be seen that this was a very unsatisfactory condition because the feed to the front end of the lead reactor was generally heated to a higher temperature than desired, and the reactants at the exit end of there-v actor were at too low a temperature to effect eihcient results. This situation could not be corrected by further preheating the feed because of the danger of thermal cracking the same to form degradation products of inferior quality.

.. The present invention involves the use of two or more eacto'rs in series, but otherwise the nature and purpose to form the corresponding aromatics in the irst reactor which as stated contains a iluidized bed of hydroforming catalyst, and thereafter the paraiiinic hydrocarbons present in the effluent from the first reactor are subjected to aromatization in a second zone under more severe conditions, particularly, at higher temperaturev conditions whereby they are first cyclisized and thereafter dehydrogenated to form additional quantities of aromatics. In the second zone, the catalyst is also in the form ofa fluidized bed, and because of this, substantially isothermal conditions areattained therein.

Another feature of the present invention involves the isomerization of non-benzenoid cyclic hydrocarbons, as for example, where ethyl cyclo-pentane is isomerized in the lead reactor to form a six-member ring naphthene and partially dehydrogenatedI therein, and. after with- 2,737,473 Patented Mar. V6, 1956 ICC drawal from the lead reactor and reheating in a furnace, is substantially completely converted to an aromatic hydrocarbon in the second or subsequent reactors.

Another feature of this invention involves, by the choice of proper feed stocks, the manufacture of benzene, toluene and the like.

Another important feature of the invention involves treatment of a mixed feed containing virgin and catalytically cracked naphtha, or, in other words, treatment of a feed to the lead reactor containing virgin naphthenic hydrocarbons, plus at least some oleiinic hydrocarbons contained in the catalytically cracked naphtha.

The main object of the present invention, therefore, is to carry out hydroforming and related processes in a continuous manner in a plurality of reactors each containing a fluidized bed of hydroforming catalyst with reheating between stages, principally characterizedin that the recycle hydrogen gas does not exceed 4000-5000 cu. ft. of hydrogen measured at standard conditions of temperature and pressure, per barrel of oil feed.

Another feature of the present invention is to regenerate the catalyst with hydrogen in the lower portion Vof the lead reactor where it is in an environment vrich in hydrogen and relatively poor in hydrocarbons.

Another feature of the present invention is to prehydrogenate the feed to the lead reactor to reduce the tendency of the operation to form excessive carbon, especially where olens are present.

Another object of the present invention has to do with carrying out hydroforming operation in a process which is more ilexible, efficient and economical than those 'heretofore commercially utilized or disclosed in prior literature. l

A simplified ilow plan depicts the essential apparatusi utilized in carrying out the present invention into elfect.

Referring in detail to the drawing a naphthenic feed preheated in a suitable heating means (not shown) enters the present system through line 1 at a temperature of the order of, say, 950 F. and is discharged into an upper section of a reactor 2 containing a fluidized bed of hydroforming catalyst C. This catalyst is in the form of a powder having a particle size of from 20G-400 mesh and consists preferably of platinum carried on active alumina also containing hydrogen fluoride, the amount of platinum being from about 0.2-1 weight per cent of the total catalyst, the hydrogen fluoride being about 0-1-.0 weight per cent of the total catalyst and the remainder being the active alumina. Palladium may be used in place of the platinum, and the carrier may be a mixture of alumina and silica. `As Vshown in the drawing, the oil vapors enter the reactor below a grid G which serves as a gas distributing means. Any other gas distributing device known in the art'may be employed. As usual, the vapors are fed through the reactor at a superficial linear velocity1 of from 0.2-1 ft.,per second so as to maintain the powdered catalyst in the uidized state mentioned. The uidized bed of catalyst has an upper dense phase level at L, above which there is disposed a light phase in which the concentration of the catalyst decreases upward. Under conditions of operation more fully set forth hereinafter, the vapors undergo conversion and issue from the dense iluidized bed toward the outlet ofthe reactor. Just prior to discharge from, the reactor, the vapors are caused to flow through one or more solidsgas separators 3 in which entrained catalyst is separated from the vapors and returned to the dense phase by one or more dip pipesd. The eluent vapors fromthe reactor are passed via line 4 to a reheat furnace 5 where they are heated to a temperature approximately 1 Superficial linear velocity is the gas or vapor velocity were there no catalyst in the reactor.

100-200 F. higher than the vapors entering the lead reactor, and thereafter these vapors are introduced into the bottom of a second reactor 7 through line 6, As usual, the reactor 7 is provided with a suitable gas distributing means G1 through which the vapors are forced and thence passed into a second body of the same catalyst Ci as that utilized in the rst reactor 2. The superficial linear velocity ofthe gases pasing through the reactor 7 is of the same order as that disclosed in connection with the description of the operation in reactor 2. During the passage of the oil vapors through the bed of catalyst C1, which has an upper dense phase level at L1, the vapors undergo conversion under conditions set forth hereinafter and then pass upwardly Afrom the dense phase toward the exit yfrom reactor 7. As before, a light catalyst dispersion in vapors is disposed above the said dense phase uid bed. As before, the vapors about to issue from the reactor 7 are ,forced through one or more gassolids separators 8 wherein entrained catalystis separated from the said vapors and returned to the dense vphase through one or more 4dip .pipes d1. The converted oil vapors are withdrawn from reactor 7 through line 9, thence passed through a catalyst separator S wherein the vapors are treated with a normally liquid oil to separate catalyst still remaining in said vapors, and the catalyst oil ,slurry thus formed is returned to reactor 7 via line 10. The vapors now substantially freed of entrained catalyst pass from separator S via line 11, through a cooler 12 and thereafter into a gas and liquid separator From separator 13 hydrogen-containing ygas having a concentration of 85% or higher is withdrawn through line 1,4, thence forced through a compressor 15, thereafter fed via line 16 into a reheat furnace 17 and eventually fed via line 18 into the bottom of reactor 2.

A portion of the gasy in line 14 is continuously rejected through line to prevent excessive buildup of this gas ,in the system, and also to permit escape from the system of sulfur compounds that may be present in the original oil feed. HReferring again to reactor 2, it will be noted that therein is disposed a body of catalyst C2, positioned in the lower part of the reactor. This catalyst also is in the form of a iluidized bed, supported on the usual grid Gs and has anA upper dense phase level at L2. This catalyst is derived from the bed of catalyst C through a pipe 19 carrying a valve V for flow control. This bed of catalyst Cz is contaminated with carbonaceous and other deposits, and is .regenerated by treatment with hydrogen at temperatures higher than those prevailing in hed Q or Ci. The. regenerated catalyst from bedI C2 passes by elutriato-n to catalyst bed C carrying `with it sensible heat, thus Vsupplying at least a portion of the heat required in the bed of catalyst C..

, Referring to bed of catalyst C. a portion of this catalyst is Withdrawn via aerated standpipe V2.1, thence dis- Charged into the vapors in line 6 and carried therewith into reactor 7. A corresponding amount of catalyst is covery equipment to the process via line 1d, controlled by a suitable valve, directly into furnace 5, also bypassing the first reactor 2. In these last two instances, however, the cracked naphtha or a specialized cut of naphtha would pass through both reactors in series.

A good way to avoid excessive carbon deposition on the catalyst is to prehydrogenate the feed if it is highly unsaturated in line 1 or lines 1 and 1a by passing the same through a hydrogenation zone where in the presence of a known hydrogenation and a fixed bed of a catalyst such as nickel or a mixture of sayl tungsten and nickel sulfide, and added hydrogen, say about 500 cubic feet per barrel of oil, the yfeed undergoes simple (not destructive) hydrogenation. A temperature of 500-800 F. and system pressure may be used in this prehydrogenation.

As previously indicated, the drawing and description thereof have not included in the interest of clarity, conwithdrawn from catalyst bed C1 via second aerated stand- I pipe, 22, discharged into vapor line 18 and returned to the catalyst bed C2 where it is subjected to regeneration in the presence of hydrogen under conditions set forth more. fully hereinafter.

A modification of the present invention involves charging to the lead reactor a mixture of virgin naphthenic feed., plus some cracked naphtha obtained from a catalytic. cracking or thermal operation. This latter portion of the feed is introduced into the present system via line 1a and thereafter via line 1 into reactor 2 with the virgin naphtha. Oleiins in the cracked naphtha are hydro. g'enated in reactor 2.

Y". Another modification of the. present invention involves feeding the virgin naphtha, or a part thereof, via line 1Cv controlled by a suitable valve directly into furnace 5, thus bypassing reactor 2, or unconverted and recycled material may likewise be returned from the product re.-

ventional accessory apparatus that would normally be employed in a plant of the character described. For example, the petroleum engineer will readily understand that in a commercial plant various ow meters, additional pumps, compressors, temperature control and recording devices, etc., would ordinarily be included as necessary and desirable accessory equipment. The final purification and recovery of the desired product would, of course, be carried out in conventional apparatus not shown in the drawing or described in words herein.

In order to illustrate the invention more fully, the following `specific examples are set forth with the understanding that the specific details are merely illustrative of the invention and the said invention is not limited to the precise details therein set forth.

EXAMPLE I vln this example, a virgin naphtha having a boiling range of from 200 to 350 F. is fed at a temperature of about 950 F. to the reactor 2 via line 1 where it is contacted with the previously disclosed platinum* catalyst. The conditions of operation are set forth below.

Temperature in reactor 2, "F. 850 Temperature in reactor 7, F. 925 Pressure in reactor 2, p. s. i. g 175 Pressure in reactor 7, p. s. i. g 150 Space velocity of feed in reactor 2, lbs. oil/hr./lb.

catalyst in reactor 4 Spacefvelocity of feed in reactor 7, lbs. oi1/hr./1b.

catalyst in reactor 2 Recycle gas (line 18), in reactor 2, cu. ft./bbl.

fresh feed 3000 Recycle gas (line 22), in reactor 7, cu. ft./bbl. fresh feed 1 3000 Catalyst/to oil ratio inreactor 2, lbs. catalyst from Cz to C/lb. feed 2 Catalyst/to oil ratio in reactor 7, lbs. catalyst from C to Ci/lb. feed l I .1 Gasfmeasured under standard conditions.

Inspection Feed Product Gravity, A. P. I 55 sa Reid Vapor Pressure- 0. 2 5. 0 Initial Boiling Point. 200 150 Final Boiling Point- 350 360 Naphthones, Wt. Perceu 45 3 Aromatics, Wt. Percent. 10 65 Parairm, Wt. Percent--. 45 32 Yield, Vol. Percent 100 88 Octane, Research, Clear 50 93 EXAMPLE 1I AIn this. example a mixture of cracked naphtha and virgin vnaphtha in the proportions of 25 vol. per cent of cracked naphtha with virgin naphtha were fed to reas, Hr* 1.o, Anos 98.5 wt. per cent.

gramas reactor 2 under the following conditions of operation -(catalyst in wt. per cent-Pt. 0,5, HF 1.0, AlzO; 98.5):

Temperature in reactor 2, "F 825 Temperature in reactor 7, F 950 Pressure in reactor 2, p. s. i. g. 175 Pressure in reactor 7, p. s. i. g 150 Space velocity of feed in reactor' 2, lbs. oil/hr./lb.

catalyst in reactor 4 Space velocity of feed in reactor 7, lbs. oil/hr./lb.

catalyst in reactor 2 Recycle gas (line 18), in reactor 2, cu.lft./bbl.

fresh feed 1 2500 Recycle gas (line 22), in reactor 7, cu.v ft./bbl.

fresh feed 1 2500 Catalyst/to oil ratio in reactor 2, lbs. catalyst from C2 to C/lb. feed 3 Catalyst/ to oil ratio in reactor 7, lbs. catalyst from C to Ci/lb. feed 1.3

1 Gas measured at standard conditions of temperature and pressure.

Inspection Feed Product 0.3 4. 0 200 160 400 410 40 4 27 69 Parafn, Wt. Percent. 33 27 Yield, Vol. Percent. 100 90 Octane, Research, Olea 57 96 EXAMPLE 11i In this example virgin. naphtha boiling within the range of from 156 to 198 F. was fed to the systemfin order to produce benzene under the following conditions of operation (catalyst same as in Example I):

Temperature in reactor 2, F. 800 Temperature in reactor 7, "F 900- Pressure in reactor 2, p. s. i. g 150 Pressure in reactor 7, p. s. i. g 135 Space velocity of feed in reactor 2, lbs. oil/hr./lb.

catalyst in reactor 2 Space velocity of feed in reactor 7, lbs. oil/hr./lb.

catalyst in reactor 1 Recycle gas (line 18), in reactor 2, cu. ft./bbl.

fresh feed 1 Recycle gas (line 22), in reactor 7, cu. ft./bbl.

fresh feedl Catalyst/ to oil ratio in reactor 2, lbs. catalyst from C2 to C/lb. feed 1.0 Catalyst/ to oil ratio in reactor 7, lbs. catalyst from C to Cr/lb. feed 1.3

1 Gas measured at standard conditions of temperature and pressure.

1(Benzene.)

In the regeneration of the catalyst conducted as indicated in bed C2 located in the lower part of reactor 2, the fouled catalyst is treated with a hydrogen-containing gas at a temperature of from about 975 to 1150 F. and, of course, under the pressure existing in reactor 2. With respect to the residence time'of the catalystl in bed C2,

it is preferable to maintain the catalyst in this bed for about 1A to 1 hour, and the catalyst is caused to remain in bed C for approximately an equivalent period of time. The ow of catalyst from bed C to bed C2 is controlled by manipulating valve V in pipe 19. Now with `respect to the temperature in bed C2 this may be controlled by the tiring in furnace 17 of the recycle gas in lines 16 and 18. If the temperature becomes too high in bed C2, a portion of the gas in line 16 may be by-passed around furnace 17.

To recapitulate bn'ey therefore the present invention constitutes the departure from prior practice in that less hydrogen than formerly required per barrel of oil is requiredfor continuous operation in the hydroforming process. Also, an important feature of the present invention is that a lower pressure may be employed. In other words, a pressure of from say -400 lbs. per square inch may be utilized in the hydroforming system as hereinbefore described, which, of course, is less than the 750 lbs. per square inch conventionally employed in this type of operation. Then, of course, as hereinbefore described the present invention utilizes the uid catalyst` technique, and is further characterized in that provision. is made for treating the catalyst which has become: fouled with a hydrogen-containing gas to regenerate orl reactivate the same.

It is to be understood that instead of using a platinum group metal other hydroforming catalysts may be used, for example, supported oxidesv of the fourth and sixth group of the periodic system.

g A good hydroforming catalyst is one containing say 10 wt. percent M003 on 90 wt. percent A1203. Furthermore, and in particular in the case of platinum where hydrogen liuoride is employed as part of the catalyst composition, it is desirable to add hydrogen iiuoride continuously to maintain the said hydrogen iiuoride on the catalyst for during the reaction there is some tendency for the catalyst to be driven olf by volatilization.

Numerous modilications of the invention may be made by those who are familiar with this art without departing from the spirit thereof.

What is claimed is:

1. A continuous method for hydroforming naphthas in a multi-stage operation carried out at a pressure of from about 100-400 p. s. i. and in which a uidized bed of a hydroforming catalyst comprising a platinum group metal carried on a carrier comprising active alumina and also containing halogen-containing material is present in each stage which comprises feeding a preheated naphtha to the first stage of the operation, simultaneously feeding to the first stage of the operation a hydrogen-containing gas, the amount of the latter being less than 5000 cu. ft. of hydrogen per barrel of oil, maintaining a relatively low hydroforming temperature, permitting the naphtha to contact the uidized bed of catalyst in the first stage under hydroforming conditions, withdrawing catalyst from the said iirst stage after it has been resident therein for an average period of time of from about lA-l hour and conducting it to a regeneration zone disposed beneath the bed of catalyst employed in the said iirst stage and treating the catalyst with a hydrogen-containing gas for an average period of time of from about 1541-1 hour to remove contaminating deposits formed by the hydroforming reaction in said first stage and returning the regenerated catalyst to said rst stage, withdrawing the products from the first stage, reheating the same to a temperature at least about 75 F. higher than that prevailing in thefirst stage, conducting the reheated products to a second hydroforming stage where they are contacted with a uidized bed of hydroforming catalyst, permitting the first stage products and the fluidized bed of catalyst to remain in contact with each other for a suiiicient period of time to complete the desired reaction, and thereafter re covering a hydroformed product.

2 fcontinuousprocessior, hydrpformingmaphthas.in., @multi/Stege onetationin whiehauidized ;bed.'0f..hyd1r0- fQfmEg Catalystis Present. yin each;stage.whichzcomnrises. fe?- illg preheatedn.aphthasotherststage,of the process.,Y sirntlltaneckzusly feedingin the `first stage ,offlthe operation aihydrogen-containingggas,Y the amount .of jthe Llatter being. fromabout 4009 to SOQOcu. ft; of ghydrogenper.. barrel o,foi15, maintaining aurelatiyely.y lowA hydroforniinguternperatnre and pressure ofk from lOOdllQyp.` s. ifilr sait?!V` IeaQtiOn 2G11@ iermtting., the naphthafta.. @maar the. uidized bed of catalyst in the first stage for a, snticient period. of ,time to effect thel .desired-ccnyersiom withdrawinacatalyst from the Saisrrst vstese afterir hasbeemresi: denttherrein for an yeragezperiod of5time of :frornabont 1/4-1l VAhour and condau'ctinggit toaregeneration lzone dis# Ped beneath the. bed i0.f-;.Ca talrs.t.; employed. in the, Said first ystagexa'nd,,Vtreatingthe catalystflrwith a hydrogen-cmJ-V` taininggas for an ayerageperiodiofdime of frornabout Wfl -hourtoremov'e contaminating deposits formed by thehydroforming reaction in saidfirstlstageand. returning thersgenerated Catalystto Saidrststaee., withdrawiaathe Ptotlu-t frOm .the .irst Stage.. reheating .the Said fprodnst. temperature'. at least bout 75 higherhamthat p1 ailing inthe first stage, conducting the'said.*retreated p roducttol arsecond hydroforming stagewhereihis contactedwith a fluidized bed of hydroformingcatalyst, rn ain,l taining a pressure of'from about IOO-AQLpas. i.4 insaid second stage, permittingltheisaid product and the uidi'zed bed ofcatalyst lto remain inY contact, .witheach ,other forl a .'suiiicie'nt" period of time toA complete .the desiredreacf.4 tion and thereafter recoveringahydroformed prodtict.

3. Thetmethodset:forthinwclairn 2in whichcatalyst isLwithdraWnlfrom the `first. stage .of the .reaction4 and delivered tothe second .stagefthe systemand simulta-T neouslyacorresnondingamount of catalyst is withdrawn from thesecond. stagevof thereaction, conductedytoy a regeneration4 zone..disposed beneath the bed of catalyst employed in thesaidrststage and. treating the fouled catalyst in the regeneration zone with a hydrogen-contain-v ing gasa for asuicient periodof time substantiallyto re- 4 more l contaminating deposits .,therefrom..

4. The method set forth inclaimwl in ,which the k feed` tQ-.thetgst fstagtofethe. prqcessfis vatmixture. of virgin naphtha. .-crackedfnaphtha..

tions sut'ablef'or reinoyingv atleast a portion of the un-y saturates .therein contai nedV priorto th'eintrodnction of said feed'fintol the saidfirst stage.

7. The methodset forth-in claim 2in whichthe feed tothe rst'stage is ltreated with hydrogenunder conditionssuitable for removing at least a portion of the unsaturates'therein cori'tained,pro`r .t th introduction of si'dlffeed into thesaid rStstage.

8. The method V'set forth in claim 1 in which thetemperature in .thefirst-.stage is of theol-der offabout 858 F. and in the second stageffthe temperature is of the order ofl aboutV 9009-9509 Ft i l 9. Themuethodlsetforthin.claim 2 in which Athe ternl perature in the tirst stage is of the order of about 850 F. and in the second stagethelternperature is of the order 0tab014t900950 Ff i 1(1).v The method set forth in claim 1 in which hydrogen merid@ isCeatiavsalr.asleflwiththeteeem139th.stesse..

11. The method set forth in claim 2 inwfhich hydrogen.l fluoride is continuously added With the feed tobothvst'ages oflfthe process.

References Cited inthe fileof this patent UNLTED STATES PATENTS OTHER 1 REFERENCES Bleus?. Ptrsleeet Proessing. wel.,` ,5, pages .35 1.'.60. 1250 

1. A CONTINUOUS METHOD FOR HYDROFORMING NAPHTHAS IN A MULTI-STAGE OPERATION CARRIED OUT AT A PRESSURE OF FROM ABOUT 100-400 P.S.I. AND IN WHICH A FLUIDIZED BED OF A HYDROFORMING CATALYST COMPRISING A PLATINUM GROUP METAL CARRIED ON A CARRIER COMPRISING ACTIVE ALUMINA AND ALSO CONTAINING HALOGEN-CONTAINING MATERIAL IS PRESENT IN EACH STAGE WHICH COMPRISES FEEDING A PREHEATED NAPHTHA TO THE FIRST STAGE OF THE OPERATION, SIMULTANEOUSLY FEEDING TO THE FIRST STAGE OF THE OPERATION A HYDROGEN-CONTAINING GAS, THE AMOUNT OF THE LATTER BEING LESS THAN 5000 CU. FT. OF HYDROGEN PER BARREL OF OIL, MAINTAINING A RELATIVELY LOW HYDROFORMING TEMPERATURE, PERMITTING THE NAPHTHA TO CONTACT THE FLUIDIZED BED OF CATALYST IN THE FIRST STAGE UNDER HYDROFORMING CONDITIONS, WITHDRAWING CATALYST FROM THE SAID FIRST STAGE AFTER IT HAS BEEN RESIDENT THEREIN FOR AN AVERAGE PERIOD OF TIME OF FROM ABOUT 1/4-1 HOUR AND CONDUCTING IT TO A REGENERATION ZONE DISPOSED BENEATH THE BED OF CATALYST EMPLOYED IN THE SAID FIRST STAGE AND TREATING THE CATALYST WITH A HYDROGEN-CONTAINING GAS FOR AN AVERAGE PERIOD OF TIME OF FROM ABOUT 1/4-1 HOUR TO REMOVE CONTAMINATING DEPOSITS FORMED BY THE HYDROFORMING REACTION IN SAID FIRST STAGE AND RETURNING THE REGENERATED CATALYST TO SAID FIRST STAGE, WITHDRAWING THE PRODUCTS FROM THE FIRST STAGE, REHEATING THE SAME TO A TEMPERATURE AT LEAST ABOUT 75* F. HIGHER THAN THAT PREVAILING IN THE FIRST STAGE, CONDUCTING THE REHEATED PRODUCTS TO A SECOND HYDROFORMING STAGE WHERE THEY ARE CONTACTED WITH A FLUIDIZED BED OF HYDROFORMING CATALYST, PERMITTING THE FIRST STAGE PRODUCTS AND THE FLUIDIZED BED OF CATALYST TO REMAIN IN CONTACT WITH EACH OTHER FOR A SUFFICIENT PERIOD OF TIMES TO COMPLETE THE DESIRED REACTION, AND THEREAFTER RECOVERING A HYDROFORMED PRODUCT. 